CN107640761B - The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material - Google Patents
The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material Download PDFInfo
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- CN107640761B CN107640761B CN201710954065.3A CN201710954065A CN107640761B CN 107640761 B CN107640761 B CN 107640761B CN 201710954065 A CN201710954065 A CN 201710954065A CN 107640761 B CN107640761 B CN 107640761B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention provides a kind of preparation methods of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material, comprising: the preparation of the graphene oxide hydrosol prepares graphene oxide using Hummer's method, graphene oxide obtained is prepared the graphene oxide hydrosol；Urea is added into the graphene oxide hydrosol of preparation, after mixing evenly, is slow added into nickel acetate, obtains precursor solution；Precursor solution is transferred in reaction kettle and is placed in isothermal reaction certain time in baking oven, graphene/carbon acid hydrogen nickel aeroge is made；Graphene/carbon acid hydrogen nickel aerogel vacuum obtained is freeze-dried, graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is made.The graphene/carbon acid hydrogen nickel composite material of preparation is applied to power lithium battery and super electric and excellent electrical property as electrode material.Preparation method reaction process of the invention is simply easily operated, low in cost and energy conservation and environmental protection, is suitble to industrial applications.
Description
Technical field
The invention belongs to nanocomposite preparation field, specially a kind of graphene/carbon acid hydrogen nickel nanocube three
The preparation method for tieing up composite material and the application on power lithium-ion battery anode and supercapacitor.
Background technique
Becoming increasingly popular from mobile electronic device to electric car, demand of the people to high performance lithium ion battery is increasingly
It is high.A large amount of research concentrates in the research of electrode new material, such as some transition metal with high theoretical capacity, oxide and
The research of carbonate becomes research hotspot.Result of study shows bicarbonate nickel compared with nickelous carbonate and other carbonate (iron, cobalt, manganese)
There is higher specific capacity as lithium electricity anode.It is hollow that 103880093 B of Chinese patent literature CN discloses a kind of bicarbonate nickel
Sphere aggregates, the patent are dissolved in water using soluble nickel salt, add carbonate deposition agent, metal chelating agent and surfactant pair
Its structure regulating has synthesized the hollow even ball aggregation of bicarbonate nickel and in ACS Energy Lett, 2017,2 (1): 111 116
In be applied to lithium electricity anode and tested (Shiqiang Zhao, Zewei Wang, Yanjie He et al.
Interconnected Ni(HCO3)2 Hollow Spheres Enabled by Self-Sacrificial Templating
with Enhanced Lithium Storage Properties. ACS Energy Letters, 2017, 2(1):
111-116), the results showed that the hollow even ball aggregation of bicarbonate nickel substantially increases the capacity and high rate performance of lithium ion battery,
However the structure destroying infection of material its cycle performance as electrode material, cause cycle performance bad.Chinese patent text
It offers 105481026 A of CN and discloses a kind of method using hydrothermal synthesis of carbon acid hydrogen nickel, specifically: ammonium nickel sulfate is dissolved
Yu Shui makes the aqueous solution of nickel salt, and then the ammonium hydrogen carbonate of a certain amount of ratio is added in nickel salt aqueous solution, is stirred at room temperature
It after mixing dissolution, is incorporated in the autoclave of polytetrafluoroethyllining lining, for airtight heating to 210 ~ 250 DEG C, heat preservation 2 ~ 8 is small
When, resulting product is filtered, is cleaned repeatedly with water, after dry, can be obtained bicarbonate nickel.Chinese patent literature CN
101962211 B disclose a kind of synthetic method of nano nickel bicarbonate, and urea or black tropine are dissolved in water first, nickel is added
Salt or nickel hydroxide dissolution, urea or black tropine and nickel ratio are 1:1 ~ 16:1, and the concentration of nickel salt is 0.1 ~ 1mol/L in solution,
Cubic phase bicarbonate nickel crystal is obtained by 90 ~ 240 DEG C of reactions in hydro-thermal 1 ~ 96 hour.The preparation process step of above-mentioned two documents
Cumbersome, raw material is more using type and product structure pattern is inhomogenous, seriously affects to properties of product and using generating, in production
It can take time and effort in the process and higher cost.It is uniform in view of the three-dimensional of pure phase graphene/carbon acid hydrogen nickel nanocube self assembly
Composite material has a wide range of applications as a kind of new function material and researching value, does not there is its correlation report also at present, because
This develops it has great significance and application value with research.
Summary of the invention
To overcome the shortcomings of the prior art, it is three-dimensional that the present invention provides a kind of graphene/carbon acid hydrogen nickel nanocube
The preparation method of composite material, and it is applied to lithium ion for the graphene/carbon acid hydrogen nickel composite material of preparation as electrode material
In battery or supercapacitor.Graphene/carbon acid hydrogen method for preparing nickel reaction process of the invention is simply easily operated, at low cost
Honest and clean and energy conservation and environmental protection is suitble to industrial applications.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material, comprising the following steps:
(1) prepared by the graphene oxide hydrosol
Graphene oxide is prepared using Hummer's method, by graphene oxide ultrasonic disperse Yu Shuizhong obtained, oxygen is made
The graphite alkene hydrosol, obtained graphene oxide hydrosol surface have negative electrical charge；
(2) prepared by graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of step (1) preparation, stirs 5 ~ 10min, is slow added into acetic acid
Nickel stirs 5 ~ 10min, obtains precursor solution；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid is made
Hydrogen nickel aeroge；
(3) prepared by graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from step (2) is embathed into removing soluble impurity through pure water, subzero 56 DEG C true
Graphene/carbon acid hydrogen nickel composite material is made in vacuum freecing-dry.
It include 0.5 in the graphene oxide hydrosol of preparation in the step (1) as currently preferred technical solution
~ 2.0g/L graphene oxide.
As currently preferred technical solution, Hummer's method prepares the specific of graphene oxide in the step (1)
Process are as follows:
1) container of dried and clean is taken, the concentrated sulfuric acid that concentration is 98% is added, container is placed on ice bath in ice water；
2) it weighs crystalline flake graphite to be added in the concentrated sulfuric acid solution for carrying out ice-water bath, then 20 ~ 30min of mechanical stirring；
3) potassium permanganate being weighed to be slowly added into the solution of step 2, when addition, is as slow as possible, become green to solution,
After potassium permanganate adds completely, then 2 ~ 3h of ice bath；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky
Yellowish-brown slurry；Container is removed water-bath, under stirring, divides 6 times, is diluted with water every time, makes sticky yellowish-brown
Slurry becomes brown solution；
4) H that mass fraction is 30% is measured2O2It is added in the brown solution of step 3), becomes golden yellow by brown to solution
Color, with golden yellow tablet；It is centrifuged again with the revolving speed of 9000r/min, incline supernatant, and sediment is with mass fraction respectively
5% dilute hydrochloric acid and deionized water respectively washs 3 times, and sample is uniformly layered on surface plate, surface plate is placed in freeze drier
It is lyophilized for 24 hours to get graphene oxide is arrived.
As currently preferred technical solution, precursor solution includes 0.5 ~ 2.0g/L graphite oxide in the step (2)
Alkene, 0.2 ~ 0.8 mol/L urea, 0.01 ~ 0.1mol/L nickel acetate.
The graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of above-mentioned preparation method preparation can be applied to lithium from
Sub- battery anode material and electrode material for super capacitor.
Compared with prior art, the invention has the benefit that
(1) the first public report graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of the present invention, preparation method and
Its application as electrode material.Bicarbonate nickel is uniformly distributed in graphene/carbon acid hydrogen nickel composite material prepared by the present invention
Between graphene layer, and there is excellent chemical property as electrode material.It is this that there is sandwich compared with existing report
The graphene/carbon acid hydrogen nickel nano cubic composite material of shape continuous passage is as novel energy-storing power battery material and catalyst
Deng with great application prospect.
(2) method of the invention for preparing graphene/carbon acid hydrogen nickel composite material is simple, easily operated, low in cost and section
Can be environmentally friendly, it is suitble to industrial applications.
(3) reaction process that the present invention prepares graphene/carbon acid hydrogen nickel composite material carries out in aqueous solution, without addition
Other auxiliary agents such as other surfactants and metal complexant, step is simple and environmentally-friendly, mild condition, low for equipment requirements, raw material
It is low in cost, it is convenient for industrial production.
(4) the graphene/carbon acid of different Ni contents is obtained by adjusting hydrothermal method process conditions in preparation process of the present invention
Hydrogen nickel nanocube three-dimensional composite material, applied to different environment.
Detailed description of the invention
Fig. 1 is graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material scanning electron microscope made from the embodiment of the present invention 1
Photo；
Fig. 2 is that graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material X-ray made from the embodiment of the present invention 1 is spread out
Penetrate figure and its comparative diagram with bicarbonate nickel crystal normal data (JCPDS No.15-0782)；
Fig. 3 is graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material transmission electron microscope made from the embodiment of the present invention 1
Photo；
Fig. 4 is graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material cyclic voltammetric made from the embodiment of the present invention 3
Figure (a, lithium electricity, b, capacitor)；
Fig. 5 is graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material different multiplying made from the embodiment of the present invention 3
Under charge and discharge electrograph (a, lithium electricity, b, capacitor).
Specific embodiment
Agents useful for same is commercial reagent in the present invention, and pure to analyze, and crystalline flake graphite specification used is 200 mesh.
The present invention provides a kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material, including with
Lower step:
The first step, the preparation of the graphene oxide hydrosol
Graphene oxide is prepared using the Hummer's method of Optimal improvements, by graphene oxide ultrasonic disperse obtained in water
In, the graphene oxide hydrosol is made；It include 0.5 ~ 2.0 g/L graphite oxide in the graphene oxide hydrosol of step preparation
Alkene, graphene oxide make its surface with negative because the oxygen-containing groups such as great amount of hydroxy group, carboxyl, carbonyl, epoxy group are contained on its surface
Charge, thus it compared with redox graphene is easier to fixing metal oxide to be used to prepare metal oxide/graphene compound
Material；
Second step, the preparation of graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of first step preparation, stirs 5 ~ 10min, is slow added into acetic acid
Nickel stirs 5 ~ 10min, obtains precursor solution；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid is made
Hydrogen nickel aeroge；
Third step, the preparation of graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from second step is embathed into removing soluble impurity through pure water, subzero 56 DEG C true
Graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is made in vacuum freecing-dry.
As one embodiment of the present invention, the Hummer's method of Optimal improvements prepares the detailed process of graphene oxide
Are as follows:
1) container of dried and clean is taken, the concentrated sulfuric acid that concentration is 98% is added, container is placed on ice bath in ice water；
2) it weighs crystalline flake graphite to be added in the concentrated sulfuric acid solution for carrying out ice-water bath, then 20 ~ 30min of mechanical stirring；
3) potassium permanganate being weighed to be slowly added into the solution of step 2, when addition, is as slow as possible, become green to solution,
After potassium permanganate adds completely, then 2 ~ 3h of ice bath；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky
Yellowish-brown slurry；Container is removed water-bath, under stirring, divides 6 times, is diluted with water every time, makes sticky yellowish-brown
Slurry becomes brown solution；
4) H that mass fraction is 30% is measured2O2It is added in the brown solution of step 3), becomes golden yellow by brown to solution
Color, with golden yellow tablet；It is centrifuged again with the revolving speed of 9000r/min, incline supernatant, and sediment is with mass fraction respectively
5% dilute hydrochloric acid and deionized water respectively washs 3 times, and sample is uniformly layered on surface plate, surface plate is placed in freeze drier
It is lyophilized for 24 hours to get graphene oxide is arrived.
It include 0.5 ~ 2.0g/L table in precursor solution obtained in the second step as one embodiment of the present invention
The negatively charged graphene oxide in face, 0.2 ~ 0.8mol/L urea, 0.01 ~ 0.1mol/L nickel acetate.
Graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material obtained above can be applied to lithium ion battery sun
Pole material and electrode material for super capacitor.
Below with reference to embodiment, the present invention is described in further detail.
Graphene oxide preparation, comprising the following steps:
1) container of dried and clean is taken, the concentrated sulfuric acid that 70ml concentration is 98% is added, container is placed on ice bath in ice water；
2) it weighs 2g crystalline flake graphite to be added in the concentrated sulfuric acid solution for carrying out ice-water bath, then mechanical stirring 30min；
3) it weighs 8g potassium permanganate to be slowly added into the solution of step 2, when addition is as slow as possible, becomes green to solution
Color, after potassium permanganate adds completely, then ice bath 3h；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky
Yellowish-brown slurry；Container is removed water-bath, under stirring, is divided 6 times, the dilution of 46ml water is added every time, makes sticky
Yellowish-brown slurry becomes brown solution；
4) H that 25ml mass fraction is 30% is measured2O2It is added in the brown solution of step 3), is become to solution by brown
Golden yellow, with golden yellow tablet；It is centrifuged again with the revolving speed of 9000r/min, incline supernatant, and sediment is respectively with quality point
Number respectively washs 3 times for 5% dilute hydrochloric acid and deionized water, and sample is uniformly layered on surface plate, surface plate is placed on freeze-drying
It is lyophilized for 24 hours in instrument to get filemot graphene oxide is arrived.
Embodiment 1
The preparation method of the graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of the present embodiment, comprising:
(1) prepared by the graphene oxide hydrosol
By graphene oxide ultrasonic disperse Yu Shuizhong obtained, the graphene oxide hydrosol of 1.0g/L is made；
(2) prepared by graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of step (1) preparation, stirs 8min, is slow added into nickel acetate,
8min is stirred, precursor solution is obtained, precursor solution includes 1.0g/L graphene oxide, 0.2mol/L urea, 0.02mol/L acetic acid
Nickel；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid is made
Hydrogen nickel aeroge；
(3) prepared by graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from step (2) is embathed into removing soluble impurity through pure water, subzero 56 DEG C true
Graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is made in vacuum freecing-dry.
The scanning electron microscope (SEM) photograph of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material prepared by the present embodiment is such as
Shown in Fig. 1, show Ni (HCO3)2Nanocube is uniformly distributed between graphene layer, and it is compound to form continuous stratiform sandwich three-dimensional
Structure.Fig. 2 is the X-ray diffractogram of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material, shows it for single-phase
Bicarbonate nickel (JCPDS:015-0782), the appearance of no graphene phase.Fig. 3 is vertical for obtained graphene/carbon acid hydrogen nickel nanometer
The transmission electron microscope picture of cube three-dimensional composite material.
Embodiment 2
The preparation method of the graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of the present embodiment, comprising:
(1) prepared by the graphene oxide hydrosol
By graphene oxide ultrasonic disperse Yu Shuizhong obtained, the graphene oxide hydrosol of 1.5g/L is made；
(2) prepared by graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of step (1) preparation, stirs 10min, is slow added into nickel acetate,
10min is stirred, precursor solution is obtained, precursor solution includes 1.5g/L graphene oxide, 0.4mol/L urea, 0.04mol/L second
Sour nickel；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid is made
Hydrogen nickel aeroge；
(3) prepared by graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from step (2) is embathed into removing soluble impurity through pure water, subzero 56 DEG C true
Graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is made in vacuum freecing-dry.
Embodiment 3
The preparation method of the graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of the present embodiment, comprising:
(1) prepared by the graphene oxide hydrosol
By graphene oxide ultrasonic disperse Yu Shuizhong obtained, the graphene oxide hydrosol of 1.5g/L is made；
(2) prepared by graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of step (1) preparation, stirs 10min, is slow added into nickel acetate,
10min is stirred, precursor solution is obtained, precursor solution includes 1.5g/L graphene oxide, 0.8mol/L urea, 0.06mol/L second
Sour nickel；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid is made
Hydrogen nickel aeroge；
(3) prepared by graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from step (2) is embathed into removing soluble impurity through pure water, subzero 56 DEG C true
Graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is made in vacuum freecing-dry.
Entire reaction process is simple in the preparation method of above-mentioned graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material
Easily operated, low in cost and energy conservation and environmental protection is suitble to industrial applications.
The electrochemistry that is used for of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material manufactured in the present embodiment is surveyed
Examination, Fig. 4 are cyclic voltammogram (a, lithium electricity, the b, electricity of obtained graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material
Container)；Fig. 5 is the charge and discharge under different multiplying of obtained graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material
Capacitance (a, lithium electricity, b, capacitor).From Fig. 4 and Fig. 5's the experimental results showed that graphene prepared by preparation method of the present invention/
Bicarbonate nickel nanocube three-dimensional composite material can be used as preparing the anode material and supercapacitor of power lithium-ion battery
Material, and there is excellent chemical property.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material, which is characterized in that including following
Step:
(1) prepared by the graphene oxide hydrosol
Graphene oxide is prepared using Hummer's method, by graphene oxide ultrasonic disperse Yu Shuizhong obtained, oxidation stone is made
The black alkene hydrosol, obtained graphene oxide hydrosol surface have negative electrical charge；
(2) prepared by graphene/carbon acid hydrogen nickel aeroge
Urea is added into the graphene oxide hydrosol of step (1) preparation, stirs 5 ~ 10min, is slow added into nickel acetate, stirs
5 ~ 10min is mixed, precursor solution is obtained；
Precursor solution is transferred in reaction kettle, reaction kettle is placed on constant temperature in 180 DEG C of baking ovens and for 24 hours, graphene/carbon acid hydrogen nickel is made
Aeroge；
(3) prepared by graphene/carbon acid hydrogen nickel composite material
Graphene/carbon acid hydrogen nickel aeroge made from step (2) is embathed into removing soluble impurity through pure water, subzero 56 DEG C of vacuum are cold
Dry obtained graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material is lyophilized.
2. a kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material according to claim 1,
It is characterized in that, including 0.5 ~ 2.0g/L graphene oxide in the graphene oxide hydrosol prepared in the step (1).
3. a kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material according to claim 1,
It is characterized in that, Hummer's method prepares the detailed process of graphene oxide in the step (1) are as follows:
1) container of dried and clean is taken, the concentrated sulfuric acid that concentration is 98% is added, container is placed on ice bath in ice water；
2) it weighs crystalline flake graphite to be added in the concentrated sulfuric acid solution for carrying out ice-water bath, then 20 ~ 30min of mechanical stirring；
3) it weighs potassium permanganate to be slowly added into the solution of step 2, when addition is as slow as possible, becomes green, Gao Meng to solution
After sour potassium adds completely, then 2 ~ 3h of ice bath；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky yellowish-brown
Color slurry；Container is removed water-bath, under stirring, divides 6 times, is diluted with water every time, makes sticky yellowish-brown pulpous state
Object becomes brown solution；
4) H that mass fraction is 30% is measured2O2It is added in the brown solution of step 3), becomes golden yellow by brown to solution,
With golden yellow tablet；It is centrifuged again with the revolving speed of 9000r/min, incline supernatant, and it is 5% that sediment uses mass fraction respectively
Dilute hydrochloric acid and deionized water respectively wash 3 times, sample is uniformly layered on surface plate, surface plate is placed in freeze drier
It is lyophilized for 24 hours to get graphene oxide is arrived.
4. a kind of preparation method of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material according to claim 1,
It is characterized in that, in the step (2) precursor solution include 0.5 ~ 2.0g/L graphene oxide, 0.2 ~ 0.8mol/L urea,
0.01 ~ 0.1mol/L nickel acetate.
5. a kind of described in any item graphene/carbon acid hydrogen nickel nanocube three-dimensional composite materials of the claims 1 ~ 4
The graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material of preparation method preparation can be applied to anode of lithium ion battery material
Material and electrode material for super capacitor.
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| CN108847482A (en) * | 2018-07-04 | 2018-11-20 | 郑州大学 | Graphene/basic carbonate cobalt nanowire three-dimensional composite material preparation method and the application in anode of lithium ion battery |
| CN109187690B (en) * | 2018-09-17 | 2020-07-07 | 洛阳理工学院 | Application of GR/PSS/Pt/GCE electrochemical sensor |
| CN109326784B (en) * | 2018-10-19 | 2021-02-02 | 郑州大学 | Phosphorus doped MoS2Preparation method and application of loaded graphene nanosheet |
| CN111106317B (en) * | 2018-10-26 | 2022-06-24 | 东丽先端材料研究开发（中国）有限公司 | Graphite oxide coated lithium ion battery anode material |
| CN110085440A (en) * | 2019-04-23 | 2019-08-02 | 中国计量大学 | A kind of nickel hydroxide/redox graphene electrode material preparation method |
| CN115594232B (en) * | 2022-10-21 | 2024-03-08 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional directional porous aerogel loaded with hollow oxide nano boxes and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN103880093A (en) * | 2014-04-15 | 2014-06-25 | 山东大学 | Hollow spherical nickel bicarbonate aggregate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN103880093A (en) * | 2014-04-15 | 2014-06-25 | 山东大学 | Hollow spherical nickel bicarbonate aggregate |
| CN103880093B (en) * | 2014-04-15 | 2015-03-11 | 山东大学 | Hollow spherical nickel bicarbonate aggregate |
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